The invention described below relates to a process for regenerating large-pore zeolite catalysts having a Group VIII metal which are used to reform petroleum feedstocks. Within the past few years such catalysts have become the object of considerable interest primarily due to their surprisingly high selectivity for paraffin dehydrocyclization to produce aromatics under low pressure reforming conditions. However, it has also been found that such catalysts are sensitive to certain types of contamination. Accordingly, there is an urgent need for a regeneration procedure for these catalysts.
During reforming, conventional catalysts become deactivated by changes in the physical state of the catalytic metal and the accumulation of carbonaceous matter (such as coke) on the catalyst surface. When deactivation occurs, it is common practice to regenerate the catalyst. U.S. Pat. No. 3,496,096 granted on Feb. 17, 1970 to Kluksdahl, describes a catalyst regeneration procedure for a platinum/rhenium catalyst. The procedure involves three steps. In the first step the catalyst is contacted with an oxygen containing gas at a temperature of less than 800.degree. F. which burns coke off the catalyst surface. In the second step the catalyst is again contacted with a gas containing oxygen and a halide, but this time the temperature is between 800.degree. F. and 900.degree. F. In the final step the catalyst is contacted with a gas having a higher oxygen concentration and halide but at a temperature above 900.degree. F. The regenerated catalyst is then contacted with a gas containing hydrogen to reduce the valence states of the oxidized platinum and rhenium. Regeneration procedures such as this one have become known in the art as oxychlorination procedures (see also U.S. Pat. No. 3,776,640 granted on Dec. 4, 1973 to Moravec et al. which describes a similar procedure for removing coke). One of their purposes is to redisperse platinum agglomerates which are formed during reforming or the coke burn.
U.S. Pat. No. 4,493,901 granted on Jan. 15, 1985 to Bernard et al. discloses a regeneration procedure for a coke deactivated zeolite reforming catalyst. Patentees use a hydration step following a coke burn and an oxychlorination step. The hydration step is carried out while contacting the catalyst with cool air after the oxychlorination step. Patentees add approximately 10 wt. % water to the cooling air.
European Patent Application 0 142 352 (Publication Number) filed on Nov. 9, 1984 broadly describes a regeneration procedure for deactivated L-zeolite catalysts. The deactivation addressed by the disclosed procedure is caused by coke deposition and platinum agglomeration. Applicants employ a coke burn step and an oxychlorination step. However, when the redispersion procedures outlined in the European patent application are attempted on catalysts that have a binder, such as silica or alumina, the activity of the regenerated catalyst is substantially lower than that of the fresh catalyst.
Sulfur may also cause catalyst deactivation. This is a particular problem for large-pore zeolite catalysts having a Group VIII metal. See U.S. Pat. No. 4,456,527 granted Jun. 26, 1984 to Buss et al.
Accordingly, there is still a need for a procedure which can restore the activity of large-pore zeolitic catalysts having an inorganic binder which have been deactivated in whole or in part by the formation of platinum agglomerates. This need has now been satisfied by the invention which is summarized and detailed below.